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Kinetics of yttrium oxide carbochlorination
The chlorination kinetics of the Y2O3-sucrose carbon system was studied by thermogravimetry. This work is a continuation of a previous one in which the reaction stages and the stoichiometry of each reaction have been determined. The influence of carbon content, total flow rate, sample initial mass and chlorine partial pressure was evaluated. The effect of carbon content on the reactive mixture was studied between 6.7 and 70% (carbon mass/total mass). The results showed that the reaction rate of each stage is strongly increased as the carbon content increases and the range of occurrence of the stages depends on the amount of carbon in the solid reactive mixture. The formation reaction of YOCl (STAGE I) is chemically controlled for temperatures lower than 700 °C with average effective activation energies of 165 ± 6 and 152 ± 7 kJ/mol for 8.7 and 16.7%C, respectively. The formation of the YOCl follows a nucleation and growth mechanism, with a combination of continuous nucleation and site saturation, and anisotropic growth controlled by diffusion. The kinetics of STAGE I can be expressed by the following global rate equation that includes the variables analyzed:dαdt=k0Bexp- EaRgTpCl2n(1-α)-ln(1-α)(n-1)/n where k0B = 1.9 × 104, n = 1.20 for 8.7%C, and k0B = 8.4 × 103, n = 1.14 for 16.7%C. STAGES II and III correspond to the YOCl carbochlorination to form YCl3, being these stages kinetically different. It was not possible to obtain kinetic parameters for these stages. The reaction rate of STAGE II is affected by diffusion of Cl2 through the gas film surrounding the sample and mass changes in STAGE III have two opposite components: formation and evaporation of liquid YCl3.
Gaviría,Fouga,Bohé
p. 24 - 33
(2011)
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Coordination between yttrium ions and amide groups of polyamide 6 and the crystalline behavior of polyamide 6/yttrium composites
Different amounts of yttrium ions were introduced into polyamide 6 (PA6) matrix by solution casting process. Structure, morphology and properties of the obtained PA6/Y3+ composite films were investigated by using FT-IR spectroscopy, Raman spectroscopy, scanning electron microscope (SEM), polarized optical microscope (POM) and differential scanning calorimeter (DSC) methods. Yttrium ions show strong coordination ability and their complexation with amide groups of PA6 can be reflected by the appearance of new bands in the amide A and amide I regions in FT-IR and Raman spectra. Furthermore, the FT-IR and Raman spectra of the PA6/Y3+ composite show that the resultant chain conformations of the amide groups in the composite films are twisted from the ideal trans conformation. The DSC results reveal that Y3+ ions cause a significant reduction of the melting point of PA6. In addition, the existence of Y3+ prevents the crystallization of molten PA6/Y3+ composite films during the cooling process. Moreover, the PA6/Y3+ composite can convert into γ phase PA6 or α phase PA6 when different solvents are used to remove Y3+ ions and induce crystallization of PA6.
Liu, Shaoxuan,Zhang, Chengfeng,Liu, Yuhai,Zhao, Ying,Xu, Yizhuang,Ozaki, Yukihiro,Wu, Jinguang
p. 63 - 69
(2012)
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Preparation of the Bis(trimethylsilyl)amido Lanthanide Chlorides 2(μ-Cl)(thf))2>(thf=tetrahydrofuran), and the Crystal and Molecular Structures of the Gadolinium and Ytterbium Complexes
Reaction of LnCl3 with 2 equivalents of LiL in tetrahydrofuran (thf) at -5 deg C yields for Ln=Eu, Gd, or Yb or for Ln=Y.X-Ray crystal structure analysis of the compounds of Gd and Yb confirms the formation of halide-bridged dimers.In the M2Cl2 bridging unit the M-Cl bond lengths differ slightly and the angle at the metal (ca. 74 deg) is much smaller than at chlorine (ca. 106 deg).The metal co-ordination geometries are irregular but can be best described as distorted trigonal bipyramidal with the bridging chlorines spanning one axial and one equatorial site.The bond lengths M-Cl and M-N indicate a Gd-Yb radius difference of ca. 0.07 Angstroem, but the M-O distances differ by 0.093 Angstroem.Variable-temperature n.m.r. studies of and show that there is free rotation about Ln-N and Ln-O bonds at room temperature.These rotations are frozen out at low temperatures to give a solution structure having higher symmetry (C2n) than that found in the crystal.
Aspinall, Helen C.,Bradley, Donald C.,Hursthouse, Michael B.,Sales, Keith D.,Walker, Nigel P. C.,Hussain, Bilquis
p. 623 - 626
(1989)
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Reduction kinetics of NiO-YSZ composite for application in solid oxide fuel cell
A porous nickel-8 mol% yttria stabilized zirconia (Ni-8YSZ) composite, used as anode for solid oxide fuel cell, was obtained by reduction of NiO-8YSZ cermet. The first goal was the evaluation of the temperature effect of powder processing by thermogravime
Yoshito,Matos,Ussui,Lazar,Paschoal
p. 303 - 308
(2009)
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Thermodynamics of lanthanide elements, IV. Molar enthalpies of formation of Y3+(aq), YCl3(cr), YBr3(cr), and YI3(cr)
Enthalpies of solution of high-purity yttrium metal and of yttrium trichloride, tribromide, and triiodide in hydrochloric acid of various molalities lead to the following standard molar enthalpies of formation ΔfH0m/(kJ *
Xiang-Yun, Wang,Zhu, Jin Tian,Goudiakas, J.,Fuger, J.
p. 1195 - 1202
(1988)
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Low-temperature heat capacity and thermochemical study of crystalline [Y2(Ala)4(H2O)8] (ClO4)6 (Ala=CH3CH(NH3+)COO-)
The solid complex of rare-earth compound with alanine, [Y2(Ala)4(H2O)8] (ClO4)6 were synthesized, and the heat capacities of the solid complex were measured with a small sample high-precision automated adiabatic calorimeter over the temperature range from 78 to 400 K. The melting point, molar enthalpy and entropy of fusion of the complex were determined to be 378.73 ± 0.01 K, 16.78 ± 0.02 kJ mol-1, 44.30 ± 0.04 JK-1 mol-1, respectively. Thermal decomposition of the complex was studied through differential scanning calorimetry (DSC) and thermogravimetry (TG). The possible mechanisms of the thermal decomposition reaction was suggested according to the TG and DSC results.
Liu, Beiping,Zhao, Xinsheng,Li, Lin,Sun, Lixian,Tan, Zhi-Cheng
p. 59 - 64
(2002)
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Effect of SiO2 on densification and microstructure development in Nd:YAG transparent ceramics
This paper examines the influence of SiO2 doping on densification and microstructure evolution in Nd3xY 3-3xAl5O12 (Nd:YAG) ceramics. Nd:YAG powders were doped with 0.035-0.28 wt% SiO2 and vacuum sintered between 1484° and 1750°C. 29Si magic-angle spinning nuclear magnetic resonance showed that Si4+ substitutes onto tetrahedrally coordinated Al3+ sites. High-resolution transmission electron microscopy showed no grain boundary second phases for all silica levels in samples sintered at 1600°-1750°C. Coarsening was limited by a solute drag mechanism as suggested by cubic grain growth kinetics and transmission electron microscopy energy-dispersive X-ray spectroscopy observations of increased Nd3+ concentration near grain boundaries. Increasing SiO2 content increased both densification and grain growth rate and led to increasingly coarsening-dominated sintering trajectories. Fine-grained (82% real in-line transmission) ceramics were produced by sintering 0.035 wt% SiO2-doped ceramics at 1750°C for 8 h. Coarse-grained (18 μm), transparent samples were obtained with 0.28 wt% SiO2-doped Nd:YAG when sintered at 1600°C for 8 h.
Stevenson, Adam J.,Li, Xin,Martinez, Miguel A.,Anderson, Julie M.,Suchy, Daniel L.,Kupp, Elizabeth R.,Dickey, Elizabeth C.,Mueller, Karl T.,Messing, Gary L.
p. 1380 - 1387
(2011)
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Carbochlorination of yttrium oxide
The reaction of chlorination of a mixture composed by Y2O 3 and sucrose carbon was studied by thermogravimetry over a temperature range of 550-950 °C. The reaction proceeds through several successive stages. The first of them is the formation of solid yttrium oxychloride (YOCl) and subsequently the YOCl is carbochlorinated to produce YCl3 (solid or liquid, depending on the temperature) in two stages. The stoichiometries of the first stage and the global reaction were estimated by mass balances, taking into account the chlorine adsorbed by the remainder carbon. The results showed that the reactions involved progress with the formation of CO2 and CO in the temperature range of 600-775 °C. The interaction between sucrose carbon and chlorine was analyzed by thermogravimetry in order to quantify the amount of chlorine which is adsorbed on its surface. It was studied the effect of the temperature and initial mass of carbon. The morphological analysis performed by SEM of partially reacted samples showed that the formation of YOCl proceeds through a mechanism of nucleation and growth. For temperatures above 715 °C the final product of the carbochlorination is liquid YCl3, whose evaporation is observed in the thermogravimetry. The evaporation kinetics was analyzed in argon atmosphere and from the thermogravimetric curves was determined a value of 250 kJ/mol for the heat of evaporation of YCl3. This value is consistent with a partial dimerization of the gaseous chloride.
Gaviría,Bohé
p. 100 - 110
(2010)
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Water-soluble Yb3+, Tm3+ codoped NaYF4 nanoparticles: Synthesis, characteristics and bioimaging
Water soluble NaYF4 nanocrystals codoped with 20 mol% Yb 3+, 0.5 mol% Tm3+ were prepared by a facile solvothermal approach using polyvinylpyrrolidone (PVP) as a surfactant. The upconversion NaYF4 nanocrystals were pure cubic phase with an average size of ～40 nm. They could be well redispersed in water to form a clearly transparent solution without obvious precipitation. With the excitation of a 980-nm diode laser, the nanocrystal solution presents bright violet and blue upconversion luminescence. These upconversion nanoparticles (UCNPs) were incubated with HeLa cells at 37 °C for 24 h, and bright blue upconversion luminescence were observed from the UCNPs endocytosed into the HeLa cells on a microscope equipped with a 980-nm fiber laser. These results indicated that the UCNPs had potential applications for biological imaging as luminescent probes.
Chen, Huan,Zhai, Xuesong,Li, Duo,Wang, Lili,Zhao, Dan,Qin, Weiping
p. 70 - 73
(2011/12/13)

Self-assembled light lanthanide oxalate architecture with controlled morphology, characterization, growing mechanism and optical property
Flower-like Sm2(C2O4)3· 10H2O had been synthesized by a facile complex agent assisted precipitation method. The flower-like Sm2(C2O 4)3·10H2O was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, thermogravimetry- differential thermal analysis and photoluminescence. The possible growth mechanism of the flower-like Sm2(C2O4) 3·10H2O was proposed. To extend this method, other Ln2(C2O4)3·nH2O (Ln = Gd, Dy, Lu, Y) with different morphologies also had been prepared by adjusting different rare earth precursors. Further studies revealed that besides the reaction conditions and the additive amount of complex agents, the morphologies of the as-synthesised lanthanide oxalates were also determined by the rare earth ions. The Sm2(C2O4) 3·10H2O and Sm2O3 samples exhibited different photoluminescence spectra, which was relevant to Sm 3+ energy level structure of 4f electrons. The method may be applied in the synthesis of other lanthanide compounds, and the work could explore the potential optical materials.
He, Hongmei,Zhang, Youjin,Zhu, Wei,Zheng, Ao
p. 1546 - 1552
(2011/10/01)

Preparation and characterization of rare earth orthoborates, LnBO 3 (Ln = Tb, La, Pr, Nd, Sm, Eu, Gd, Dy, Y) and LaBO3:Gd, Tb, Eu by metathesis reaction: ESR of LaBO3:Gd and luminescence of LaBO3:Tb, Eu
Lanthanide orthoborates of composition LnBO3 (Ln = Tb, La, Pr, Nd, Sm, Eu, Gd, Dy, Y) and LaBO3:Gd, Tb, Eu have been prepared by metathesis reaction. This method provides a convenient route for the synthesis of orthoborates and its solid solutions at low temperatures. Powder X-ray diffraction and FT-IR spectroscopy were used to characterize these borates. Rare earth borates, (LnBO3) are isomorphous with different forms of CaCO3 depending on the radius of rare earth ion. LaBO3, LaBO3:Gd, Tb, Eu, PrBO3, NdBO3 crystallized in aragonite structure, SmBO3 crystallized in H-form and TbBO 3, EuBO3, GdBO3, DyBO3, YBO 3 crystallized in vaterite structure. The structural analysis of TbBO3 was carried out. The morphology of these borates was obtained from Scanning electron microscopy. Spin-Hamiltonian parameters for Gd 3+ are deduced from room temperature electron spin resonance spectrum of LaBO3:Gd. The luminescence of LaBO3:Tb, Eu gave characteristics peaks corresponding to Tb3+, Eu3+ respectively.
Velchuri, Radha,Kumar, B. Vijaya,Devi, V. Rama,Prasad,Prakash, D. Jaya,Vithal
p. 1219 - 1226
(2011/07/09)

Lanthanide carbonates
The crystal and molecular structures of the rare earth carbonates with the general formulae [C(NH2)]3 [Ln(CO3)4 (H2O)]·2H2O (where Ln = Pr3+,Nd 3+,Sm3+,Eu3+,Gd3+,Tb 3+)and [C(NH2)]3 [Ln(CO3) 4]·2H2O (where Ln = Y3+,Dy 3+,Ho3+,Er3+, Tm3+,Yb 3+,Lu3+) were determined. The crystals consist of monomeric [Ln(CO3)4 (H2O)] 5-or [Ln(CO3)4] 5-complex anions in which the carbonate ligands coordinate to the Ln3+ion in a bidentate manner. The spectroscopic (UV/Vis/NIR and IR) properties of the crystalline lanthanide carbonates, as well as their aqueous solutions, were determined. Correlation between the spectroscopic and the structural data enabled us to conclude that the [Ln(CO3)4 (OH)]6-and [Ln-(CO 3)4]5- species predominate in the light and heavy lanthanide solutions, respectively. The nature of the Ln-O interaction was also discussed. The experimental data, as well as the theoretical calculations, indicated that the Ln-O(CO3 2-) bond is more covalent than the Ln-O(OH2) bond. Moreover, the covalency degree is larger for the heavy lanthanide ions. Inspection of the NBO results revealed that the oxygen hybrids, with the approximate composition sp4, form strongly polarized bonds with the 6s6p5d4 hybrids of lutetium. 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Janicki, Rafal,Starynowicz, Przemyslaw,Mondry, Anna
p. 3601 - 3616
(2011/10/11)

Synthesis, characterization and thermal behaviour of solid-state tartrates of heavy trivalent lanthanides and yttrium(III)
Solid state Ln2-L3 compounds, where Ln stands for heavy trivalent lanthanides (terbium to lutetium) and yttrium, and L is tartrate [(C4H4O6)-2] have been synthesized. Simultaneous thermogra
Ambrozini, B.,Dametto, P. R.,Ionashiro, M.
p. 867 - 871
(2011/10/31)

Synthesis, characterization and thermal behaviour of heavy lanthanide and yttrium pyruvates in the solid state
Solid-state Ln-L compounds, where Ln stands for heavy trivalent lanthanides or yttrium (III) (Tb-Lu, Y) and where L is pyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-R
Siqueira,De Carvalho,Rodrigues,Ionashiro,Bannach,Ionashiro
p. 95 - 100
(2010/08/05)

Synthesis, characterization and thermal behaviour of solid-state 3-methoxybenzoates of heavy trivalent lanthanides and yttrium(III)
Solid-state Ln(L)3 compounds, where Ln stands for trivalent Tb, Dy, Ho, Er, Tm, Yb, Lu and Y, and L is 3-methoxybenzoate, have been synthesized. X-ray powder diffractometry, infrared spectroscopy, complexometry and elemental analysis were used to characterize the compounds. Inorder to study the thermal behaviour of these compounds simultaneous th ermogravimetry and differential thermal analysis (TG-DTA) and differential scanning calorimetry (DSC) were used. The results provided information on the composition, dehydration, polymorphic transformation, thermal stability and thermal decomposition of the synthesized compounds.
Dametto, P. R.,Ambrozini, B.,Siqueira, A. B.,Carvalho, C. T.,Ionashiro, M.
p. 933 - 940
(2011/01/06)

Structural characterization of methanol substituted lanthanum halides
The first study into the alcohol solvation of lanthanum halide [LaX3] derivatives as a means to lower the processing temperature for the production of the LaBr3 scintillators was undertaken using methanol (MeOH). Initially the de-hydration of {[La(μ-Br)(H2O)7](Br)2}2 (1) was investigated through the simple room temperature dissolution of 1 in MeOH. The mixed solvate monomeric [La(H2O)7(MeOH)2](Br)3 (2) compound was isolated where the La metal center retains its original 9-coordination through the binding of two additional MeOH solvents but necessitates the transfer of the innersphere Br to the outersphere. In an attempt to in situ dry the reaction mixture of 1 in MeOH over CaH2, crystals of [Ca(MeOH)6](Br)2 (3) were isolated. Compound 1 dissolved in MeOH at reflux temperatures led to the isolation of an unusual arrangement identified as the salt derivative {[LaBr2.75·5.25(MeOH)]+0.25 [LaBr3.25·4.75(MeOH)]-0.25} (4). The fully substituted species was ultimately isolated through the dissolution of dried LaBr3 in MeOH forming the 8-coordinated [LaBr3(MeOH)5] (5) complex. It was determined that the concentration of the crystallization solution directed the structure isolated (4 concentrated; 5 dilute) The other LaX3 derivatives were isolated as [(MeOH)4(Cl)2La(μ-Cl)]2 (6) and [La(MeOH)9](I)3·MeOH (7). Beryllium Dome XRD analysis indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR (139La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4-6 were slightly higher in comparison to their hydrated counterparts.
Boyle, Timothy J.,Ottley, Leigh Anna M.,Alam, Todd M.,Rodriguez, Mark A.,Yang, Pin,Mcintyre, Sarah K.
p. 1784 - 1795
(2010/07/03)

Versatile synthesis strategy for carboxylic acid-functionalized upconverting nanophosphors as biological labels
Up-converting rare-earth nanophosphors (UCNPs) have great potential to revolutionize biological luminescent labels, but their use has been limited by difficulties in obtaining UCNPs that are biocompatible. To address this problem, we have developed a simple and versatile strategy for converting hydrophobic UCNPs into water-soluble and carboxylic acid-functionalized analogues by directly oxidizing oleic acid ligands with the Lemieux-von Rudloff reagent. This oxidation process has no obvious adverse effects on the morphologies, phases, compositions and luminescent capabilities of UCNPs. Furthermore, as revealed by Fourier transform infrared (FTIR) and NMR results, oleic acid ligands on the surface of UCNPs can be oxidized into azelaic acids (HOOC(CH2) 7COOH), which results in the generation of free carboxylic acid groups on the surface. The presence of free carboxylic acid groups not only confers high solubility in water, but also allows further conjugation with biomolecules such as streptavidin. A highly sensitive DNA sensor based on such streptavidin-coupled UCNPs have been prepared, and the demonstrated results suggest that these biocompatible UCNPs have great superiority as luminescent labeling materials for biological applications.
Chen, Zhigang,Chen, Huili,Hu, He,Yu, Mengxiao,Li, Fuyou,Zhang, Qiang,Zhou, Zhiguo,Yi, Tao,Huang, Chunhui
p. 3023 - 3029
(2008/09/19)

2-Methoxybenzylidenepyruvatewith heavier trivalent lanthanides and yttrium(III): Synthesis and characterization
Solid-state Ln(2-MeO-BP) compounds, where Ln stands for trivalent Eu to Lu and Y(III) and 2-MeO-BP (which is 2-methoxybenzylidenepyruvate) have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanni
Ionashiro,Bannach,Siqueira,De Carvalho,Rodrigues,Ionashiro
p. 953 - 959
(2009/02/01)

Solubility behavior of rare earths with ammonium carbonate and ammonium carbonate plus ammonium hydroxide: Precipitation of their peroxicarbonates
The purpose of this work is to report the significant behavior of the rare earths when treated with ammonium carbonate and with a binary mixture of ammonium carbonate plus ammonium hydroxide. The carbonates of some rare earths are completely soluble in ammonium carbonate or in ammonium carbonate plus ammonium hydroxide, while others are only partially soluble and finally some are completely insoluble. Addition of hydrogen peroxide to the soluble complexed rare earth carbonates results in the precipitation of a series of a new compounds described as rare earth peroxicarbonates. The rare earths have some different precipitation behavior in the carbonate-peroxide system. Some are completely and immediately precipitated, others are completely precipitated after an aging period, and finally other are not precipitated at all. These different behaviors open a new possibility for the separation chemistry of the rare earths. Sm, Gd, Dy, Y, Yb and Tm are fast and completely soluble in ammonium carbonate. Ho, Eu and Tb are completely soluble in ammonium carbonate but slowly dissolved. La, Ce, Pr and Nd are only partially soluble in ammonium carbonate. While Ce, Pr, Nd, Sm, Eu and Dy are completely and easily soluble in the ammonium carbonate plus ammonium hydroxide mixture, La is only partially soluble and Tb is completely insoluble in the same mixture. Concerning the peroxicarbonates, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy and Ho are quantitatively precipitated. The precipitation of the Er peroxicarbonate is quantitative, but after an aging period of 24 h. Y is not precipitated at all. The process is very easy, simple and economically attractive. Although proved in bench scale, its scale-up is easily feasible.
de Vasconcellos, Mari E.,da Rocha,Pedreira,Queiroz, Carlos A. da S.,Abr?o, Alcídio
p. 426 - 428
(2008/10/09)

Synthesis, characterization and thermal behaviour of solid 2-methoxybenzoates of trivalent metals
Solid-state Ln(L)3 compounds, where Ln stands for trivalent Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y and L is 2-methoxybenzoate have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanni
Siqueira,Carvalho,Ionashiro,Bannach,Rodrigues,Ionashiro
p. 945 - 951
(2009/02/01)

Synthesis, potentiometric, kinetic, and NMR studies of 1,4,7,10- tetraazacyclododecane-1,7-bis(acetic acid)-4,10-bis(methylenephosphonic acid) (DO2A2P) and its complexes with Ca(II), Cu(II), Zn(II) and lanthanide(III) ions
A cyclen-based ligand containing trans-acetate and trans- methylenephosphonate pendant groups, H6DO2A2P, was synthesized and its protonation constants (12.6, 11.43, 5.95, 6.15, 2.88, and 2.77) were determined by pH-potentiometry and 1H NMR spectroscopy. The first two protonations were shown to occur at the two macrocyclic ring N-CH 2-PO32- nitrogens while the third and fourth protonations occur at the two phosphonate groups. In parallel with protonation of the two -PO32- groups, the protons from the NH +-CH2-PO32- are transferred to the N-CH2-COO- nitrogens. The stability constants of the Ca2+, Cu2+, and Zn2+ (ML, MHL, MH2L, and M2L) complexes were determined by direct pH-potentiometry. Lanthanide(III) ions (Ln3+) form similar species, but the formation of complexes is slow; so, out-of-cell pH-potentiometry (La 3+, Eu3+, Gd3+, Y3+) and competitive spectrophotometry with Cu(II) ion (Lu3+) were used to determine the stability constants. By comparing the log KML values with those of the corresponding DOTA (H4DOTA = 1,4,7,10-tetraazacyclododecane-1,4, 7,10-tetraacetic acid) and DOTP (H8DOTP = 1,4,7,10- tetraazacyclododecane-1,4,7,10-tetramethylenephosphonic acid) complexes, the order DOTA 2+ complexes, for which the order is reversed. The relaxivity of Gd(DO2A2P) decreases between pH 2 and 7 but remains constant in the pH range of 7 1 = 3.6 mM-1 s-1). The linewiths of the 17O NMR signals of water in the absence and presence of Gd(DO2A2P) (at pH = 3.45 and 8.5) between 274 and 350 K are practically the same, characteristic of a q = 0 complex. Detailed kinetic studies of the Ce3+ and Gd3+ complexes with DO2A2P showed that complex formation is slow and involves a high stability diprotonated intermediate Ln(H2DO2A2P)*. Rearrangement of the diprotonated intermediate into the final complex is an OH- assisted process but, unlike formation of Ln(DOTA) complexes, rearrangement of Ln(H2DO2A2P)* also takes place spontaneously likely as a result of transfer of one of the protons from a ring nitrogen to a phosphonate group. The order of the OH- assisted formation rates of complexes is DOTA > DO2A2P > DOTP while the order of the proton assisted dissociation rates of the Gd3+ complexes is reversed, DOTP > DO2A2P > DOTA. 1H and 13C NMR spectra of Eu(DO2A2P) and Lu(DO2A2P) were assigned using two-dimensional correlation spectroscopy (2D COSY), heteronuclear multiple quantum coherence (HMQC), heteronuclear chemical shift correlation (HETCOR), and exchange spectroscopy (EXSY) NMR methods. Two sets of 1H NMR signals were observed for Eu(DO2A2P) characteristic of the presence of two coordination isomers in solution, a twisted square antiprism (TSAP) and a square antiprism (SAP), in the ratio of 93% and 7%, respectively. Line shape analysis of the 1H NMR spectra of Lu(DO2A2P) gave lower activation parameters compared to La(DOTP) for interconversion between coordination isomers. This indicates that the Ln(DO2A2P) complexes are less rigid probably due to the different size and spatial requirements of the carboxylate and phosphonate groups.
Kalman, Ferenc K.,Baranyai, Zsolt,Toth, Imre,Banyai, Istvan,Kiraly, Robert,Bruecher, Ernoe,Aime, Silvio,Sun, Xiankai,Sherry, A. Dean,Kovacs, Zoltan
p. 3851 - 3862
(2009/02/02)

A systemic study of stepwise chlorination-chemical vapor transport characteristics of pure rare earth oxides from Sc2O3 to Lu2O3 mediated by alkaline chlorides as complex former
A systematic study has been carried out for the stepwise chlorination-chemical vapor transport (SC-CVT) characteristics of pure rare earth oxides from Sc2O3 to Lu2O3 mediated by the vapor complexes KLnCl4 and NaLnCl4 (Ln = Sc, Y and La-Lu) used NaCl and KCl as complex former, respectively. The results showed that the SC-CVT characteristics are similarly for NaCl and KCl as complex former, the main deposition temperature of the rare earth chlorides LnCl3 is in the increasing order ScCl3 3 3, and then with a systematically decreasing trend from the early lanthanide chlorides to the end one. The results also showed that the total transported amount of the produced chlorides is YCl3 > ScCl3, and they are much higher than that of most lanthanoid chlorides. For lanthanoids, the total transported amount of chloride increases systematically from the early lanthanoid chlorides to the end one except for EuCl3 and GdCl3 mediated by KCl and NaCl as complex former, respectively, which showed the divergence effect of Gd in the total transport efficiency. But there are some differences in SC-CVT characteristics of pure rare earth oxide mediated by KCl and NaCl as complex former, that is the main deposition temperature region for the same rare earth element was lower for KCl than that for NaCl as complex former except for LaCl3, CeCl3, YbCl3 and LuCl3, while the total transport amount of rare earth chloride for KCl as complex former is higher than that for NaCl except for LaCl3 and EuCl3. More over, the discussion was carried out for Sc and Y on the one hand and the lanthanides contain 4f electron as another hand based on the 4f electron hybridization assumption. Further more, the transport characteristics of rare earth oxides with alkaline chlorides as complex former in this study were compared to that with AlCl3 as complex former.
Sun, Yan-Hui,He, Peng,Chen, Hua-Ni
p. 352 - 358
(2008/10/09)

Synthesis, characterization and thermal behaviour of solid-state compounds of yttrium and lanthanide benzoates
Solid-state Ln(Bz)3?H2O compounds where Ln stands for trivalent yttrium or lanthanides and Bz is benzoate have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), X-ray powder diffractometry, infra
Locatelli,Rodrigues,Siqueira,Ionashiro,Bannach,Ionashiro
p. 737 - 746
(2008/10/09)

Phosphinic derivative of DTPA conjugated to a G5 PAMAM dendrimer: An 17O and 1H relaxation study of its Gd(III) complex
A DTPA-based chelate containing one phosphinate group was conjugated to a generation 5 polyamidoamine (PAMAM) dendrimer via a benzylthiourea linkage. The Gd(iii) complex of this novel conjugate has potential as a contrast agent for magnetic resonance imaging (MRI). The chelates bind Gd3+ via three nitrogen atoms, four carboxylates and one phosphinate oxygen, and one water molecule completes the inner coordination sphere. The monomer Gd(iii) chelates bearing nitrobenzyl and aminobenzyl groups ([Gd(DTTAP-bz-NO2)(H 2O)]2- and [Gd(DTTAP-bz-NH2)(H 2O)]2-) as well as the dendrimeric Gd(iii) complex G5-(Gd(DTTAP))63) were studied by multiple-field, variable temperature 17O and 1H NMR. The rate of water exchange is faster than that of [Gd(DTPA)(H2O)]2- and very similar on the two monomeric complexes (8.9 and 8.3 × 106 s-1 for [Gd(DTTAP-bz-NO2)(H2O)]2- and [Gd(DTTAP-bz-NH2)(H2O)]2-, respectively), while it is decreased on the dendrimeric conjugate (5.0 × 106 s -1). The Gd(iii) complex of the dendrimer conjugate has a relaxivity of 26.8 mM-1 s-1 at 37 °C and 0.47 T (corresponding to 1H Larmor frequency of 20 MHz). Given the contribution of the second sphere water molecules to the overall relaxivity, this value is slightly higher than those reported for similar size dendrimers. The experimental 17O and 1H NMR data were fitted to the Solomon-Bloembergen-Morgan equations extended with a contribution from second coordination sphere water molecules. The rotational dynamics of the dendrimeric conjugate was described in terms of global and local motions with the Lipari-Szabo approach. The Royal Society of Chemistry 2006.
Lebdukova, Petra,Sour, Angelique,Helm, Lothar,Toth, Eva,Kotek, Jan,Luke, Ivan,Merbach, Andre E.
p. 3399 - 3406
(2007/10/03)

Luminescent properties of yttrium diphenylphosphinate activated by europium
The synthesis and spectroscopic characterization of yttrium diphenylphosphinates doped with europium are reported. The purity of all samples was confirmed by carbon and hydrogen micro analysis, thermal analysis, IR vibrational spectroscopy, and X-ray diff
Francisco, Cristina S.,Stucchi, Elizabeth B.,de Abreu, Edson M.
p. 234 - 237
(2008/10/09)

Equilibria and structure of the lanthanide(III)-2-hydroxy-1,3- diaminopropane-N,N,N′,N′-tetraacetate complexes: Formation of alkoxo-bridged dimers in solid state and solution
The complex formed between 1,3-diamino-2-hydroxypropane-N,N,N′, N′-tetraacetic acid (H4L-OH) and Nd3+ at pH 7.5 was found to be a dinuclear dimer in the solid state by X-ray crystallography. In the complex K4[Nd2(L-O)2-(H2O) 2]-14H2O each ligand is coordinated to both Nd 3+ atoms with an iminodiacetate group (the Nd3+-Nd 3+ distance is 3.9283(8) A). The alcoholic OH groups are deprotonated, and the alkoxo oxygens are coordinated to both Nd3+ in a bridging position. The Nd3+ ions are nine-coordinated with one water molecule per Nd(III) ion in the inner sphere. The complex K 4[Nd2(L-O)2(H2O)2] ·14H2O has an inversion center, and the space group is P1. Two of the K+ counterions are six-coordinated, while the other two K+ ions are eight-coordinated; polar polymeric water-K+ layers are formed between the apolar ligand layers via the bridging water molecules. The dinuclear dimer complexes are also present in aqueous solution. The proton relaxivities of the Gd3+ complex decrease with the increase of pH, and at pH > 6, the low relaxivity values indicate the probable absence of H2O in the inner sphere and the predominance of the eight-coordinated dimer species [Gd2(L-O)2]. 4- The results of ESI-TOF MS studies of the complexes of La 3+, Nd3+, and Lu3+ proved the formation of dinuclear dimers in dilute (0.25 mM) solutions. pH-potentiometric titrations indicate the formation of complexes with 1:1 (Ln(L-OH)-, Ln(HL-OH), and Ln2(L-O)24-) and 2:1 (Ln 2(L-O)+) metal-to-ligand ratios. The stability constants of the Ln(L-OH)- species increase from La3+ (log K = 10.19) to Lu3+ (log K = 14.08). The alcoholic OH group of the Ln(L-OH)- species dissociates at unusually low pH values. The pH range of dissociation shifts to lower and lower pH's with the increasing atomic number of the lanthanides. This pH range is about 4-7 for the La3+ complex and 1-4 for the Lu3+ complex. The results of 1D and 2D 1H and 13C NMR studies of the La3+ complex, the number and multiplicity of signals, and the values of coupling constants are in agreement with the dinuclear dimer structure of the complex in solution.
Tircso, Gyula,Benyei, Attila,Bruecher, Erno,Kis, Anita,Kiraly, Robert
p. 4951 - 4962
(2008/10/09)

Comparative study of the mutual separation characteristics for binary mixed oxides Er2O3-Ln2O3 (Ln = Sc, Y, La, Nd, Sm, Gd and Ho) mediated by vapor complexes KLnCl4
Mutual separation characteristics for a series of rare earth elements Sc, Y, La, Nd, Sm, Gd, Ho and Er from their binary oxide mixtures Er 2O3-Sc2O3, Er2O 3-Y2O3, Er2O3-La 2O3, Er2O3-Nd2O 3, Er2O3-Sm2O3, Er 2O3-Gd2O3 and Er2O 3-Ho2O3 has been investigated using a stepwise chlorination-chemical vapor transport (SC-CVT) reaction mediated by vapor complexes KLnCl4. The total transported yield of the chlorides produced from the oxide mixtures was in the order of ErCl3 > ScCl3, ErCl3 > YCl3, ErCl3 > LaCl3, ErCl3 > NdCl3, ErCl3 > SmCl3, ErCl3 > GdCl3 and HoCl3 > ErCl3, and the total separation factors are 13.0 for Er:Sc, 1.49 for Er:Y, 1.48 for Er:La, 1.15 for Er:Nd, 2.33 for Er:Sm, 2.72 for Er:Gd and 1.10 for Ho:Er. The largest separation factors 1213.8 for Er:Sc, 6.37 for Er:Y, 189.3 for Er:La, 100.6 for Er:Nd, 105.7 for Er:Sm, 27.8 for Er:Gd and 1.14 for Er:Ho in the lower temperature region, while 102.7 for La:Er, only 14.3 for Nd:Er, 16.7 for Sm:Er, 4.0 for Gd:Er and 2.04 for Ho:Er in the higher temperature region were observed, respectively. The results showed the obvious divergence effect of Gd both in the largest separation factors, the total separation factors and total transport efficiency. Furthermore, the results were discussed on the difference of ionic radius of Sc and Y on the one side and the lanthanoid elements of La, Nd, Sm, Gd, Ho and Er on the other hand, and verified that the ionic radius is one of the decisive factors only for lanthanide elements, not for Sc and Y.
Sun, Yan-Hui,Chen, Zhen-Fei,Hu, Sheng-Liang
p. 175 - 180
(2008/10/09)

Trimethylyttrium and trimethyllutetium
(Chemical Equation Presented) Complexes in disguise: Homoleptic [Ln(AlMe4)3] (Ln = Y, Lu) complexes are effectively masked [LnMe3]n species, which are produced reversibly upon equimolar addition of a Lewis base to the former. Compounds [LnMe 3]n are thermally stable and readily form peralkylated heterobimetallic complexes with alkylaluminum, -gallium, and -magnesium reagents (see scheme).
Dietrich, H. Martin,Raudaschl-Sieber, Gabriele,Anwander, Reiner
p. 5303 - 5306
(2007/10/03)

Lanthanide contraction and pH value controlled structural change in a series of rare earth complexes with p-aminobenzoic acid
A series of rare earth complexes with p-aminobenzoic acid (HL) have been synthesized: [RE2L6(H2O)2] n [RE=La (1), Ce(2), Pr(3), Sm(4), Eu(5), Tb(6), Dy(7), Er(9)] and [RE2L6(H2O)4]·2H 2O [RE=Tb(6′), Ho(8), Yb(10), Lu(11), Y(12)]. The crystal structures of 1, 2, 6, 6′, 7, 9 and 12 have been determined and the isomorphous relationships of the others have been identified. Their structures change from two-dimensional (2D) array (the coordination number of the metal ions is nine for 1 and eight for 2-7 and 9) to double-nuclear structure (the metal ions are eight-coordinated) for 6′, 8 and 10-12, as controlled by lanthanide contraction. The structural type has been found influenced by the pH value of the reaction mixtures.
Sun, Hao-Ling,Ye, Chao-Hong,Wang, Xin-Yi,Li, Jun-Ran,Gao, Song,Yu, Kai-Bei
p. 77 - 83
(2007/10/03)

Effect of solid matrices on the luminescence of europium(III) tungstate
The effect of natural and synthetic zeolites, CaCO3, and crystalline zirconium phosphate on the luminescence intensity of europium tungstate sorbates was studied in comparison to europium(III)-doped Mg, Ca, Sr, Ba, La, Gd, and Y tungstates prepared by coprecipitation with tungstate anion. The effects of the alkaline-earth cation, metal salt anion, coprecipitation conditions, and calcination temperature on the luminescence were revealed. X-ray powder diffraction showed that the resulting compounds have a scheelite structure. The luminescence intensity of Eu(III)-doped Ca tungstate under the identical conditions of short-wave excitation (λex = 254 nm) makes up 33% of the intensity exhibited by the commercial FL-612 red-emitting phosphor.
Topilova,Meshkova,Dotsenko,Kovalevskaya,Kiriyak,Malinka,Efryushina
p. 1932 - 1935
(2008/10/09)

Fullerides: Heterometallic superconductors with composition M2M′C60 (M = K, Rb; M′ = Yb, Lu, Sc)
One- or two-step reactions of potassium and rubidium fullerides with composition Mk C60 (M = K, Rb; k = 3-6) and K 6C60 + m K mixtures (m = 1, 3) with anhydrous salts M′Cl3 (M′ = La, Pr, Nd, Sm, Gd, Tb, Yb, Lu, Y, Sc) and YbI2 in a toluene-THF medium afforded heterometallic fullerides M3- n M′n C60 (n = 1-3). Among these compounds, substituted fullerides with composition M2M′C60 (M′ = Yb, Lu, Sc) display superconducting properties with critical temperatures of 14-20 K.
Bulychev,Lunin,Kul'bachinskii,Shpanchenko,Privalov
p. 1686 - 1692
(2007/10/03)

Calorimetric study and thermal analysis of [Gd4/3Y2/3(Gly)6 (H2O)4](ClO4) 6·5H2O and [ErY(Gly)6(H2O)4] (ClO4)6·5
Two solid-state coordination compounds of rare earth metals with glycin, [Gd4/3Y2/3(Gly) 6(H2O)4](ClO4) 6·5H2O and [ErY(Gly)6(H2O)4] (
Liu, Bei-Ping,Tan, Zhi-Cheng,Lan, Xiao-Zheng,Yu, Hua-Guang,Zhang, Da-Shun,Sun, Li-Xian
p. 233 - 238
(2008/10/08)

Organometallic compounds of the lanthanides. 168 [1]: Lanthanidocene complexes containing sulfur-functionalized cyclopentadienyl ligands
YCl3, SmCl3, and LuCl3 react with 2 equivalents of Na[C5H4CH2CH2SR] (R = Ph (2); Et (3)) yielding (PhSCH2CH2C5H 4)2LnCl (Ln = Y (4a), Sm (4b), Lu (4c)), and (EtSCH 2CH2C5H4)2LuCl (5), respectively. Methylation of 4a, 4c, and 5 with LiMe produces (PhSCH 2CH2C5H4)2LnMe (Ln = Y (6a); Lu (6c)) and (EtSCH2CH2C5H 4)2LuMe (7). YCl3 and LuCl3 react with 1 equivalent of 2 or 3 followed by 1 equivalent Na[C5Me 5] to give (PhSCH2CH2C5H 4)(C5Me5)LnCl (Ln = Y (8a); Lu (8c)) and (EtSCH2CH2C5H4)(C5Me 5)YCl (9). [(EtSCH2CH2C5H 4)(C5Me5)LuCl (10) and 1,10-bipyridine form [(EtSCH2CH2C5H4)-(C 5Me5)Lu(bipy)]+ [(EtSCH2CH 2C5H4)(C5Me5)LuCl 2]- (11). Methylation of 8a, 8c, and 9 with LiMe results in the formation of (PhSCH2CH2C5H 4)(C5Me5)LnMe (Ln = Y (12a); Lu (12c)) and (EtSCH2CH2C5H4)(C5Me 5)YMe (13). LaCl3 and PrCl3 react with 3 equivalents of 3 affording (EtSCH2CH2C5H 4)3Ln (Ln = La (14d) and Pr (14e)), while the reaction of YbI2 with 2 equivalents of 3 gives [(EtSCH2CH 2C5H4)Yb(SCH2CH2C 5H4)]2 (15) along with ethane. The structures of 8c, 11, 14d, and 15 were determined by single-crystal X-ray diffraction.
Schumann, Herbert,Herrmann, Katja,Muehle, Stefan H.,Dechert, Sebastian
p. 1184 - 1194
(2008/10/08)

Thermochemical investigations on the systems RE2O3-SeO2 IV. Solution calorimetry of the phases RE2SexO3+2x (RE = Nd, Sm, Y)
The solution enthalpies have been determined for the ternary phases RE2SexO3+2x existing on the pseudo-binary section RE2O3-SeO2 and for RE2O3 and SeO2 in 4
Zhang-Pre?e,Oppermann
p. 661 - 667
(2007/10/03)

Synthesis, characterisation and thermal behaviour of solid stat compounds of 4-methylbenzylidenepyruvate with heavier trivalent lanthanides and yttrium(III)
Solid state Ln-4-Me-BP compounds, where Ln stands for heavier trivalent lanthanides (gadolinium to lutetium) and yttrium(III) and 4-Me-BP is 4-methylbenzylidenepyruvate (CH3-C6H4-CH=CH-COCOO-), have been synthesized. Eleme
Marques,Melios,Ionashiro
p. 145 - 150
(2008/10/08)

Synthesis and Olefin polymerization catalysis of new trivalent samarium and yttrium complexes with bridging bis(cyclopentadienyl) ligands
New trivalent samarium and yttrium complexes with bridging bis(cyclopentadienyl) ligands were synthesized, and olefin polymerization catalysis of the complexes having an alkyl group [R = CH(SiMe3)2] on the metal was investigated. Three types of the rare earth halides (rac, C1, and meso) whose structures differed with respect to the bridging group and the positions of substituents on the cyclopentadienyl (Cp) rings were prepared: rac-Sm-Cl, Me2Si[2,4-(Me3Si)2C5 H2]2SmCl2Li(THF)2 (1a); C1-Sm-Cl, Me2Si[2,4-(Me3Si)2 C5H2][3,4-(Me3Si)2C5 H2]-SmCl2Li(THF)2 (2a); C1(Ph2Si)-Sm-Cl, Ph2Si[2,4- (Me3Si)2C5H2][3,4- (Me3Si)2C5H2]SmCl2- Li(THF)2 (3); meso-Sm-Cl, [1,2-(Me2Si)(Me2SiOSiMe2)](4-Me3 CC5H2)2SmCl2Li(THF)2 (4a);rac-Y-Cl, Me2Si[2,4-(Me3Si)2C5 H2]2YCL2Li(THF)2 (5a); C1-Y-Cl, Me2Si[2,4-(Me3Si)2 C5H2][3,4-(Me3Si)2C5 H2]YCl2Li(THF)2 (6a); meso-Y-Cl, [1,2-(Me2Si)(Me2SiOSiMe2)](4-Me3 SiC5H2)2YCl-(THF) (7a). Although the rac and C1 complexes (1a, 2a and 5a, 6a) were obtained as an isomeric mixture by the reaction of LnCl3 (Ln = Sm, Y) with a dilithium salt of the ligand Me2Si[(Me3Si)2C5 H3]2, it could be separated into both the pure complexes by utilizing the difference of solubility in hexane in each case. Structural data were obtained on 1a, 2a, 3, and 7a to confirm the structures expected from NMR spectroscopy. The (ring centroid)- metal-(ring centroid) angles in these complexes are ca. 10-20° smaller than those in nonbridging bis(cyclopentadienyl) rare earth complexes. The rare earth halides 1a, 2a, 4a, 5a, 6a, and 7a reacted with LiCH(SiMe3)2 to afford rare earth alkyl complexes, rac-Sm-R, Me2Si[2,4-(Me3Si)2C5 H2]2SmCH(SiMe3)2 (1b); C1-Sm-R, Me2Si[2,4-(Me3Si)2 C5H2][3,4-(Me3Si)2C5 H2]SmCH(SiMe3)2 (2b); meso-Sm-R, [1,2-(Me2Si)(Me2SiOSiMe2)] (4-Me3CC5H2)2SmCH (SiMe3)2 (4b); rac-Y-R, Me2Si[2,4-(Me3Si)2C5 H2]2YCH(SiMe3)2 (5b); C1-Y-R, Me2Si[2,4-(Me3Si)2 C5H2][3,4-(Me3Si)2C5 H2] YCH(SiMe3)2 (6b); meso-Y-R, and [1,2-(Me2Si)(Me2SiOSiMe2)] (4-Me3SiC5H2)2YCH (SiMe3)2 (7b), respectively. Only C1 type alkyl complexes (2b and 6b) polymerize ethylene, giving high molecular weight polyethylenes, and the precise structure of the active Sm complex 2b was determined by X-ray crystallography.
Ihara, Eiji,Yoshioka, Shiro,Furo, Masahito,Katsura, Kenji,Yasuda, Hajime,Mohri, Shouhei,Kanehisa, Nobuko,Kai, Yasushi
p. 1752 - 1761
(2008/10/08)

Comparative study for stepwise chlorination-chemical vapor transport characteristics of pure rare earth oxides from Sc2O3 to Lu2O3 mediated by the vapor complexes LnAlnCl3n+3
A systematic study has been carried out for the stepwise chlorination-chemical vapor transport (SC-CVT) characteristics of pure rare earth oxides from Sc2O3 to Lu2O3 mediated by the vapor complexes LnAlnCl3n+3 (where Ln = rare earth elements) under identical conditions. The results show that the total transported amount of the produced chlorides is the highest for YCl3; it is also high for ScCl3, but low for LaCl3, and then increases systematically from the early lanthanide chlorides to the end lanthanide chlorides except CeCl3, EuCl3 and GdCl3. The results also show that the main deposition temperature of the chlorides is in the increasing order ScCl3 3 3 and then with a systematically decreasing trend from the early lanthanide chlorides to the end lanthanide chlorides. Based on the literature data for the solid complexes LnAl3Cl12 and LnAl3Br12, a similar coordination structure assumption is introduced for the vapor complexes LnAl3Cl3n+3 from Ln = Sc to Ln = Lu with the same stoichiometry to explain the SC-CVT characteristics of the pure rare earth oxides from Sc2O3 to Lu2O3 using a 4f electron hybridization assumption.
Wang, Zhi-Chang,Sun, Yan-Hui,Guo, Lei
p. 109 - 113
(2008/10/08)

Synthesis, characterization and anticoagulant action of lanthanide complexes of warfarin
Thirteen lanthanide complexes of warfarin, LnL3·nH2O [n = 6 (Ln = La-Yb) or n = 4 (Ln = Y); L = (C19H15O4)-] have been synthesized and characterized by elemental analyses, IR, 1H
Jiao, Tian Quan,Wu, Ji Gui,Zeng, Fu Li,Fu, Yun Long,Deng, Ru Wen
p. 725 - 735
(2008/10/09)

Ternary chlorides in the systems ACl/YCl3 (A = Cs, Rb, K, Na)
Phase diagrams of the pseudobinary systems ACl/ YCl3 (A = Cs, Rb, K, Na) were investigated by DTA and XRD. In all systems compounds of the type A3YCl6 and AY2Cl7 are formed. Furthermore the chlorides A2YCl5 exist with A = Cs, Rb and K, and Cs3Y2Cl9 and NaYCl4 were found. The unit cells of compounds with still unknown structure, were determined by X-ray diffraction on crystal powders. By a combination of solution calorimetry and e.m.f. measurements in galvanic cells for solid electrolytes thermodynamic functions for the formation of AnYCln+3 from (nACl + YCl3) were measured. The compounds Cs3Y2Cl9, Rb2YCl5 and K3YCl6 are stable in competition with the adjacent compounds in their systems only at temperatures >0 K. The systems AClYCl3 are only gradually different from the systems ACl/HoCl3.
Seifert,Büchel
p. 342 - 348
(2008/10/09)

Thermal decomposition of rare earth complexes with 2-amino-3,5-dichlorobenzoic acid
The conditions of the thermal decomposition of the 2-amino-3,5-dichloro-benzoates of Y and lanthanides have been studied. During heating in air, the dihydrated complexes Ln(C6H2Cl2NH2COO) 3·2H2/
Mrozek,Sikorska,Rzaczynska
p. 707 - 720
(2008/10/09)

Thermodynamic study of the rare earth vapour complexes: ScAl2Cl9 and YAl2Cl9
In all previous publications dealing with LnAlnCl3n+3 (Ln = rare earth elements), the LnAl3Cl12 complex is established to be the main vapour complex in the temperature range 500-900 K. Here we present results fr
Wang, Zhi-Chang,Wang, Lin-Shan,Gao, Rong-Jie,Su, Yi
p. 1887 - 1890
(2007/10/03)

Chemical Transport of Yttrium Trichloride by Aluminium Trichloride
Yttrium trichloride is transported by gaseous aluminium trichloride in the temperature range of 300°C to 700°C from hot to cold. It is followed a gaseous complex YAl4Cl15(g), and the enthalpy of formatio as well as the standard entropy of the complex from
Oppermann, H.,Huong, D. Q.
(2008/10/08)

Investigation on the Thermal Decomposition of Ammonium Yttrium Halides. I. Ammonium Yttrium Chlorides
(NH4)3YCl6 decomposes in first step to the solid phase NH4Y2Cl7 (s) and gaseous NH3(g) and HCl(g). NH4Y2Cl7(g) decomposes in a second step to YCl3, NH3 and HCl. The decomposition-pressure-functions are given and fromthis the enthalpies of formation and standard entropies of the phases a re derived.
Oppermann, H.,Huong, D. Q.
(2008/10/08)

LANTHANIDE COMPLEXES OF DI(4-HYDROXYCOUMARINYL-3)-ACETIC ACID AND THEIR ANTICOAGULANT ACTION
The lanthanide complexes of di(4-hydroxycoumarinyl-3)-acetic acid (M2L3*10H2O) have been synthesized and characterized by IR, HNMR, electronic spectra, thermoanalysis and molar conductance.The metallic ions substituted two hydrogen atoms of carboxyl and hydroxy groups and are also bonded to the oxygen atom of the carbonyl group of the benzopyranyl ring.Electronic spectra showed that the lanthanide-ligand bond had some covalent character and the involvement of 4f orbital was very small.The light lanthanide complexes revealed the nice anticoagulant action especially the lanthanum coordination compound.
Deng, Ru Wen,Wu, Ji Gui,Long, La Sheng
p. 439 - 444
(2007/10/02)

Halide alkoxides of yttrium, gadolinium, erbium and ytterbium
Reactions of yttrium, gadolinium, erbium and ytterbium isopropoxides with acetyl halides (chloride and bromide) in different molar ratios lead to respective halide isopropoxides containing increasing amounts of ester in the form of addition products.Chloride isopropoxides have also been prepared by radical interchange reactions between lanthanide trihalides and trisopropoxides.A typical 'gadolinium break' is observed in the solubilities of these products.The reactions of lanthanide t-butoxides with acetyl chloride are rather complex; the lanthanide chlorides formed initially tend to react with the side-product t-butyl acetate to form acetoxy derivatives, indicating an interesting variation with the change in the electronegativity values of the metals.
Mehrotra, R.C.,Batwara, J.M.,Tripathi, U.D.,Tripathi, U.M.
p. 793 - 798
(2007/10/02)

The low-temperature heat capacity of yttrium trichloride
The heat capacity of yttrium has been investigated in the temperature range 11 - 310 K by adiabatic calorimetry.The thermodynamic functions under standard conditions have been determined.
Tomach, P I,Gorbunov, V E,Gavrichev, K S,Goryushkin, V F
p. 579 - 580
(2007/10/02)

A new yttrium sesquichloride nitride, β-Y2Cl3N, that is isostructural with the binary yttrium sesquichloride
Reactions of YCl3, YN, and Y metal in sealed Nb containers over a range of temperatures and compositions afford β-Y2Cl3N, whereas only α-Y2Cl3N in the (α-)Gd2Cl3N structure is obtained in the absence of metal. β-Gd2Cl3N is synthesized similarly. The β-Y2Cl3N (β-Gd2Cl3N) gives a powder pattern that is indistinguishable from that of the infinite cluster chain phase Y2Cl3 (Gd2Cl3) except for small increases in lattice parameters corresponding to a 2% (1%) increase in cell volume. (α-Y2Cl3N: a = 12.761 (1) A?, b = 6.676 (2) A?, c = 6.1000 (7) A? (Pbcn). β-Y2Cl3N: a = 15.248 (2) A?, b = 3.8520 (4) A?, c = 10.157 (2) A?, β = 118.41° (C2/m, Z = 4). β-Gd2Cl3N: α = 15.290 (5) A?, b = 3.912 (1) A?, c = 10.209 (3) A?, β = 117.79 (3)°.) A single-crystal X-ray study of β-Y2Cl3N (R = 3.9%, Rw = 4.8%) demonstrates that the nitrogen atoms are positioned in tetrahedral metal sites above and below the shared metal edges of the infinite chain of octahedra found in Y2Cl3. The need for metal in the syntheses, the black color of the fibrous crystals, and the refined occupancy of nitrogen (81 (2)%) in the yttrium phase all suggest a small nitrogen deficiency in β-(Y,Gd)2Cl3N. The close correspondence of distances in the binary vs the ternary (β) sesquichlorides, particularly the small (0.024 A?) increase in the shared Y-Y edge, is discussed.
Meyer, H.-Jürgen,Jones, Nancy L.,Corbett, John D.
p. 2635 - 2637
(2008/10/08)